Ethylene glycol dinitrate

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Ethylene glycol dinitrate
Ethylene glycol dinitrate.svg
Ethylene glycol dinitrate 3D ball.png
Names
Preferred IUPAC name
Ethane-1,2-diyl dinitrate
Other names
Ethylene glycol dinitrate, Glycol dinitrate, Ethylene dinitrate, Ethylene nitrate, 1,2-Bis(nitrooxy)ethane, Nitroglycol (NGc), 1,2-Ethanediol dinitrate, Dinitroglycol, EGDN, Ethane-1,2-diyl dinitrate
Identifiers
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.010.058 OOjs UI icon edit-ltr-progressive.svg
PubChem CID
UNII
  • InChI=1S/C2H4N2O6/c5-3(6)9-1-2-10-4(7)8/h1-2H2 Yes check.svgY
    Key: UQXKXGWGFRWILX-UHFFFAOYSA-N Yes check.svgY
  • InChI=1/C2H4N2O6/c5-3(6)9-1-2-10-4(7)8/h1-2H2
  • O=N(=O)OCCON(=O)=O
  • C(CO[N+](=O)[O-])O[N+](=O)[O-]
Properties
C2H4N2O6
Molar mass 152.1 g/mol
AppearanceOily, colorless to light yellow liquid
Odor odorless [1]
Density 1.4918 g/cm3
Melting point −22.0 °C (−7.6 °F; 251.2 K)
Boiling point 197.5 °C (387.5 °F; 470.6 K)
5 g/l
Vapor pressure 0.05 mmHg (@ 20 °C) [1]
Explosive data
Shock sensitivity 0.02 kp m = 0.2 Nm
Friction sensitivity 36 kp = 353 N pistil load no reaction
Detonation velocity 7300  m/s [2]
Hazards
GHS labelling:
GHS-pictogram-flamme.svg GHS-pictogram-skull.svg GHS-pictogram-silhouette.svg GHS-pictogram-explos.svg
NFPA 704 (fire diamond)
2
1
4
Flash point 215 °C; 419 °F; 488 K [1]
NIOSH (US health exposure limits):
PEL (Permissible)
C 0.2 ppm (1 mg/m3) [skin] [1]
REL (Recommended)
ST 0.1 mg/m3 [skin] [1]
IDLH (Immediate danger)
75 mg/m3 [1]
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
X mark.svgN  verify  (what is  Yes check.svgYX mark.svgN ?)

Ethylene glycol dinitrate, abbreviated EGDN and NGC, also known as Nitroglycol, is a colorless, oily, explosive liquid obtained by nitrating ethylene glycol. It is similar to nitroglycerine in both manufacture and properties, though it is more volatile and less viscous. Unlike nitroglycerine, the chemical has a perfect oxygen balance, meaning that its ideal exothermic decomposition would completely convert it to low energy carbon dioxide, water, and nitrogen gas, with no excess unreacted substances, without needing to react with anything else.

Contents

History and production

Pure EGDN was first produced by the Belgian chemist Louis Henry (1834–1913) in 1870 by dropping a small amount of ethylene glycol into a mixture of nitric and sulfuric acids cooled to 0 °C. [3] The previous year, August Kekulé had produced EGDN by the nitration of ethylene, but this was actually contaminated with beta-nitroethyl nitrate. [4] [5] [6]

Other investigators preparing NGc before publication in 1926 of Rinkenbach's work included: Champion (1871), Neff (1899) & Wieland & Sakellarios (1920), Dautriche, Hough & Oehme.

The American chemist William Henry Rinkenbach (1894–1965) prepared EGDN by nitrating purified glycol obtained by fractioning the commercial product under pressure of 40mm Hg, and at a temperature of 120°. For this 20g of middle fraction of purified glycol was gradually added to mixture of 70g nitric acid and 130g sulfuric acid, maintaining the temperature at 23°. The resulting 49g of crude product was washed with 300ml of water to obtain 39.6g of purified product. The low yield so obtained could be improved by maintaining a lower temperature and using a different nitrating acid mixture. [5]

1) Direct Nitration of Glycol is carried out in exactly the same manner, with the same apparatus, and with the same mixed acids as nitration of glycerine. In the test nitration of anhydrous glycol (100g) with 625g of mixed acid HNO
3 40% & H
2SO
4 60% at 10-12°, the yield was 222g and it dropped to 218g when the temp was raised to 29-30°. When 500g of mixed acid HNO
3 50% & H
2SO
4 50% was used at 10-12°, the yield increased to 229g. In commercial nitration, the yields obtained from 100 kg anhydrous glycol and 625 kg of mixed acid containing HNO
3 41%, H
2SO
4 58% & water 1% were 222.2 kg of NGc at nitrating temp of 10-12° and only 218.3 kg at 29-30°. This means 90.6% of theory, as compared to 93.6% with NG.

C2H4(OH)2 + 2 HNO3 → C2H4(ONO2)2 + 2 H2O

or through the reaction of ethylene oxide and dinitrogen pentoxide:

C2H4O + N2O5 → C2H4(ONO2)2

2) Direct Production of NGc from Gaseous Ethylene.

3) Preparation of NGc from Ethylene Oxide.

4) Preparation of NGc by method of Messing from ethylene through chlorohydrin & ethylene oxide.

5) Preparation of NGc by duPont method.

Properties

Physical properties

Ethylene glycol dinitrate is a colorless volatile liquid when in pure state, but is yellowish when impure.

Molar weight 152.07, N 18.42%, OB to CO2 0%, OB to CO +21%; colorless volatile liquid when in pure state; yellowish liquid in crude state; sp gr 1.488 at 20/4° or 1.480 at 25°; n_D 1.4452 at 25° or 1.4472 at 20°; freezing point -22.75° (versus +13.1° for NG); frozen point given in [7] is -22.3°; boiling point 199° at 760mm Hg (with decomposition).

Brisance by lead block compression (Hess crusher test) is 30.0 mm, versus 18.5 mm for NG and 16 mm for TNT (misleading, needs to give exact density and mass of explosive (25 or 50 g). Brisance by sand test, determined in mixtures with 40% kieselguhr, gave for NGc mixtures slightly higher results then with those containing NG.

Chemical properties

When ethylene glycol dinitrate is rapidly heated to 215 °C, it explodes; this is preceded by partial decomposition similar to that of nitroglycerin. EGDN has a slightly higher brisance than nitroglycerin.

Ethylene glycol dinitrate reacts violently with potassium hydroxide, yielding ethylene glycol and potassium nitrate:

C2H2(ONO2)2 + 2 KOH → C2H2(OH)2 + 2 KNO3

Other

EGDN was used in manufacturing explosives to lower the freezing point of nitroglycerin, in order to produce dynamite for use in colder weather. Due to its volatility it was used as a detection taggant in some plastic explosives, e.g. Semtex, to allow more reliable explosive detection, until 1995 when it was replaced by dimethyldinitrobutane. It is considerably more stable than glyceryl trinitrate owing to the lack of secondary hydroxyl groups in the precursor polyol.

Like other organic nitrates, ethylene glycol dinitrate is a vasodilator.

See also

Related Research Articles

<span class="mw-page-title-main">Explosive</span> Substance that can explode

An explosive is a reactive substance that contains a great amount of potential energy that can produce an explosion if released suddenly, usually accompanied by the production of light, heat, sound, and pressure. An explosive charge is a measured quantity of explosive material, which may either be composed solely of one ingredient or be a mixture containing at least two substances.

<span class="mw-page-title-main">Nitroglycerin</span> Chemical compound

Nitroglycerin (NG), also known as trinitroglycerin (TNG), nitro, glyceryl trinitrate (GTN), or 1,2,3-trinitroxypropane, is a dense, colorless, oily, explosive liquid most commonly produced by nitrating glycerol with white fuming nitric acid under conditions appropriate to the formation of the nitric acid ester. Chemically, the substance is an organic nitrate compound rather than a nitro compound, but the traditional name is retained. Invented in 1847 by Ascanio Sobrero, nitroglycerin has been used ever since as an active ingredient in the manufacture of explosives, namely dynamite, and as such it is employed in the construction, demolition, and mining industries. Since the 1880s, it has been used by militaries as an active ingredient and gelatinizer for nitrocellulose in some solid propellants such as cordite and ballistite. It is a major component in double-based smokeless propellants used by reloaders. Combined with nitrocellulose, hundreds of powder combinations are used by rifle, pistol, and shotgun reloaders.

Nitric acid is the inorganic compound with the formula HNO3. It is a highly corrosive mineral acid. The compound is colorless, but older samples tend to be yellow cast due to decomposition into oxides of nitrogen. Most commercially available nitric acid has a concentration of 68% in water. When the solution contains more than 86% HNO3, it is referred to as fuming nitric acid. Depending on the amount of nitrogen dioxide present, fuming nitric acid is further characterized as red fuming nitric acid at concentrations above 86%, or white fuming nitric acid at concentrations above 95%.

<span class="mw-page-title-main">TNT</span> Impact-resistant high explosive

Trinitrotoluene, more commonly known as TNT, more specifically 2,4,6-trinitrotoluene, and by its preferred IUPAC name 2-methyl-1,3,5-trinitrobenzene, is a chemical compound with the formula C6H2(NO2)3CH3. TNT is occasionally used as a reagent in chemical synthesis, but it is best known as an explosive material with convenient handling properties. The explosive yield of TNT is considered to be the standard comparative convention of bombs and asteroid impacts. In chemistry, TNT is used to generate charge transfer salts.

<span class="mw-page-title-main">Ethylene glycol</span> Organic compound ethane-1,2-diol

Ethylene glycol is an organic compound with the formula (CH2OH)2. It is mainly used for two purposes, as a raw material in the manufacture of polyester fibers and for antifreeze formulations. It is an odorless, colorless, flammable, viscous liquid. Ethylene glycol has a sweet taste, but it is toxic in high concentrations.

<span class="mw-page-title-main">Dinitrogen tetroxide</span> Chemical compound

Dinitrogen tetroxide, commonly referred to as nitrogen tetroxide (NTO), and occasionally (usually among ex-USSR/Russia rocket engineers) as amyl, is the chemical compound N2O4. It is a useful reagent in chemical synthesis. It forms an equilibrium mixture with nitrogen dioxide. Its molar mass is 92.011 g/mol.

<span class="mw-page-title-main">Ethylene oxide</span> Cyclic compound (C2H4O)

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<span class="mw-page-title-main">Hydrazoic acid</span> Unstable and toxic chemical compound

Hydrazoic acid, also known as hydrogen azide or azoimide, is a compound with the chemical formula HN3. It is a colorless, volatile, and explosive liquid at room temperature and pressure. It is a compound of nitrogen and hydrogen, and is therefore a pnictogen hydride. It was first isolated in 1890 by Theodor Curtius. The acid has few applications, but its conjugate base, the azide ion, is useful in specialized processes.

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Mannitol hexanitrate is a powerful explosive. Physically, it is a powdery solid at normal temperature ranges, with density of 1.73 g/cm3. The chemical name is hexanitromannitol and it is also known as nitromannite, MHN, and nitromannitol, and by the trademarks Nitranitol and Mannitrin. It is more stable than nitroglycerin, and it is used in detonators.

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<span class="mw-page-title-main">Propylene glycol dinitrate</span> Chemical compound

Propylene glycol dinitrate (PGDN, ttup 1,2-propylene glycol dinitrate, or 1,2-propanediol dinitrate) is an organic chemical, an ester of nitric acid and propylene glycol. It is structurally similar to nitroglycerin, except that it has one fewer nitrate group. It is a characteristically and unpleasantly smelling colorless liquid, which decomposes at 121 °C, below its boiling point. It is flammable and explosive. It is shock-sensitive and burns with a clean flame producing water vapor, carbon monoxide, and nitrogen gas.

Tetranitromethane or TNM is an organic oxidizer with chemical formula C(NO2)4. Its chemical structure consists of four nitro groups attached to one carbon atom. In 1857 it was first synthesised by the reaction of sodium cyanoacetamide with nitric acid.

Oxygen balance is an expression that is used to indicate the degree to which an explosive can be oxidized. If an explosive molecule contains just enough oxygen to fully oxidize the other atoms in the explosive. For example, fully oxidized carbon forms carbon dioxide, hydrogen forms water, sulfur forms sulfur dioxide, and metals form metal oxides. A molecule is said to have a positive oxygen balance if it contains more oxygen than is needed and a negative oxygen balance if it contains less oxygen than is needed.

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<span class="mw-page-title-main">Acetyl nitrate</span> Chemical compound

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References

  1. 1 2 3 4 5 6 NIOSH Pocket Guide to Chemical Hazards. "#0273". National Institute for Occupational Safety and Health (NIOSH).
  2. ↑ Meyer, M.; Köhler, J.; Homburg, A. (2007). Explosives (6th ed.). WILEY-VCH. p. 227. ISBN   978-3-527-31656-4.
  3. ↑ L. Henry (1870) "Untersuchungen über die Aetherderivate der mehratomigen Alkohole und Säuren (Vierter Theil.)" (Investigations of ether derivatives of polybasic alcohols and polyprotic acids (fourth part)), Berichte der deutschen chemischen Gesellschaft, 3 : 529–533.
  4. ↑ Wieland, H.; Sakellarios, E. (1920). "Die Nitrierung des Äthylens" [The nitration of ethylene]. Berichte der Deutschen Chemischen Gesellschaft. 53 (2): 201–210. doi:10.1002/cber.19200530211.
  5. 1 2 Rinkenbach, W. H. (1926). "The Properties of Glycol Dinitrate". Industrial and Engineering Chemistry. 18 (11): 1195–1197. doi:10.1021/ie50203a027.
  6. ↑ A. Kekulé (1869) "Ueber eine Verbindung des Aethylens mit Salpetersäure" (On a compound of ethylene with nitric acid), Berichte der deutschen chemischen Gesellschaft, 2 : 329–330.
  7. ↑ Curme, G. O.; Johnston, F., eds. (1952). Glycols. American Chemical Society Monograph. Vol. 114. Reinhold. pp. 65–7, 130–134, 312. OCLC   558186858.
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